Refined heavy alkylate bottoms oil

ABSTRACT

A COLORLESS AND ODORLESS SPECIALTY OIL HAVING A VISCOSITY WITHIN THE RANGE FROM ABOUT 75 SSU TO ABOUT 3000 SSU AT 100*F., A VISCOSITY INDEX WITHIN THE RANGE FROM ABOUT 0 TO ABOUT -200, AND AN AROMATICS CONTENT COMPARABLE TO THAT OF WHITE OILS IS PREPARED BY HYDROGEN REFINING AND THEN DYDROGENATING A HEAVY ALKYLATE BOTTOMS OIL OF APPROXIMATELY THE SAME VISCOSITY AND VISCOSITY INDEX WHICH HAS A BOILING RANGE WITHIN THE LIMITS FROM ABOUT 540*F. TO ABOUT 800*F. THE HEAVY ALKYLATE OIL CONTAINS AT LEAST ABOUT 90 WEIGHT PRECENT SATURATED HYDROCARBONS, WHICH ARE ABOUT 50 TO 70 WEIGHT PERCENT NAPHTHENES, THE REMAINDER BEING ISOPARAFFINS. THESE SATURATED MOLECULES HAVE HIGHLY BRANCHED SIDE CHAINS WHICH ARE CHARACTERIZED BY A HIGH &#34;BRANCHINESS RATIO&#34; OF FROM ABOUT 2.6 TO ABOUT 3.9 THE NAPHTHENES ARE PREDOMINANTLY POLYCYCLIC AND HAVE A BICYCLIC RATIO OF FROM ABOUT 0.4 TO ABOUT 0.8. HYDROGEN REFINING OF THE HEAVY ALKYLATE OIL IS CARRIED OUT IN THE PRESENCE OF A SULFUR-INSENSITIVE CATALYST AT A TEMPERATURE FROM ABOUT 400*F. TO ABOUT 700*F. UNDER A HYDROGEN PRESSURE FROM ABOUT 150 TO ABOUT 2000 P.S.I.G. USING A HYDROGEN-TREAT RATE FROM ABOUT 100 TO ABOUT 1000 S.C.F./BBL. AT A LIQUID HOURLY SPACE VELOCITY FROM ABOUT 0.1 TO ABOUT 10. HYDROGENATION OF THE HYDROGENREFINED HEAVY ALKYLATE OIL OCCURS IN A HYDROGENATION ZONE OVER A GROUP VIII METAL HYDROGENATION CATALYST AT TEMPERATURES FROM ABOUT 300*F. TO ABOUT 650*F., A HYDROGEN PRESSURE FROM ABOUT 300 TO ABOUT 3000 P.S.IG., A LIQUID HOURLY SPACE VELOCITY FROM ABOUT 0.1 TO ABOUT 3.0 V./V./HR., AND A HYDROGEN-TREAT RATE FROM ABOUT 300 TO ABOUT 2500 S.C.F./BBL. THE HYDROGENATED OIL IS USEFUL AS A UNIQUE COSMETIC BASE OIL.

Dub 1972 "r. L. ASHCRAFT, JR 3,105,093

REFINED HEAVY ALKYLATE BOTTOMS OIL Filed June 14, 1971 HYDROGENR-EFINING l6 5 I ZONE HEAVY AL l YhATE BOTTOMS HYDROGENATION ZONE 4 OILUSEFUL AS COSMETIC OIL INVENTOR. THOMAS L. ASHCRAFT,

AT ORNEY.

United States Patent O U.S. Cl. 208-14 17 Claims ABSTRACT OF THEDISCLOSURE A colorless and odorless specialty oil having a viscositywithin the range from about 75 SSU to about 3000 SSU at 100 F., aviscosity index within the range from about to about -200, and anaromatics content comparable to that of white oils is prepared byhydrogen refining and then hydrogenating a heavy alkylate bottoms oil ofapproximately the same viscosity and viscosity index which has a boilingrange within the limits from about 540 F. to about 800 F. The heavyalkylate oil contains at least about 90 weight percent saturatedhydrocarbons, which are about 50 to 70 weight percent naphthenes, theremainder being isoparaffins. These saturated molecules have highlybranched side chains which are characterized by a high branchiness ratioof from about 2.6 to about 3.9. The naphthenes are predominantlypolycyclic and have a bicyclic ratio of from about 0.4 to about 0.8.Hydrogen refining of the heavy alkylate oil is carried out in thepresence of a sulfur-insensitive catalyst at a temperature from about400 F. to about 700 F. under a hydrogen pressure from about 150 to about2000 p.s.i. g. using a hydrogen-treat rate from about 100 to about 1000s.c.f./bbl. at a liquid hourly space velocity from about 0.1 to about10. Hydrogenation of the hydrogenrefined heavy alkylate oil occurs in ahydrogenation zone over a Group VIII metal hydrogenation catalyst attemperatures from about 300 F. to about 650 F., a hydrogen pressure fromabout 300 to about 3000 p.s.i.g., a liquid hourly space velocity fromabout 0.1 to about 3.0 v./v./hr., and a hydrogen-treat rate from about300 to about 2500 s.c.f./bbl. The hydrogenated oil is useful as a uniquecosmetic base oil.

CROSS-REFERENCE TO RELATED APPLICATION This is a continuation-in-partapplication of Serial No. 11,606 filed Feb. 16, 1970 and now abandoned,entitled Refined Heavy Alkylate Bottoms Oil.

BACKGROUND OF THE INVENTION This invention is directed to specialty oilswhich are useful as cosmetic oils and methods of producing such oils.More particularly, the invention concerns the hydrogen treatment of aheavy alkylate bottoms oil having a boiling range within the limits fromabout 540 F. to about 800 F., a viscosity index within the range fromabout 0 to about 200, and a viscosity within the range from about 75 SSUto about 3000 SSU at 100 F.

Heretofore, specialty oils used as cosmetic base oil have been preparedfrom virgin fractions of paraffinic and naphthenic distillates by acidtreatments, hydrogen treatments, or both. The viscosities of these oilshave ranged from about 75 SSU and lower up to about 500 SSU at ice 100F., the lowest viscosity indexes being about 70. Also, specialty oilscharacterized as colorless and odorless have been produced from heavyalkylate oils boiling in the range from 450 F. to 650 F. and having aviscosity at 100 F. of 48 and 52 SSU, as in U.S. Pat. 3,121,678.Heretofore, however, no specialty oil usable as a cosmetic oil base hasbeen prepared from heavy alkylate bottom oils which have a boiling rangewithin the limits from about 540 F. to about 800 F., and which, I havediscovered, have highly unusual viscosity characteristics for an oilessentially composed, as I have found them to be, of saturatedhydrocarbons. These unusual characteristics are a viscosity within therange from about 75 SSU to about 3000 SSU at 100 F. and a viscosityindex of from about 0 to about 20().

SUMMARY OF THE INVENTION In brief, my invention involves a two-stagehydrogen treatment of a heavy alkylate bottoms oil having a boilingrange within the limits from about 540 F. to about 800 F., a viscositywithin the range from about SSU to about 3000 SSU at 100 F., and aviscosity index within the range from about 0 to about -200. The oil isfirst hydrogen refined under certain prescribed conditions, hereinafterdetailed, in the presence of a sulfur-insensitive catalyst to removesulfur and nitrogen in the oil. Thereafter, it is hydrogenated in thepresence of a Group VIII metal catalyst under hydrogenation conditions,hereinafter described which produce a colorless and odorless oil withvery low aromatic compound content and possessing the unusual viscositycharacteristics of the heavy alkylate bottoms oil from which it isprepared, making the oil so produced particularly useful as a uniquecosmetic base oil.

The heavy alkylate bottoms oil employed The heavy alkylate bottoms oilsemployed in my invention are a by-product of the well-known acid(usually sulfuric acid) catalyzed isobutane or isopentane alkylation ofC to C olefins, being the portion remaining after the alkylationreaction products are fractionally distilled to recover the productsboiling below about 540 F. These heavy alkylate bottoms oils generallydistill in an ASTM D-1l60 distillation above about 540 F. and belowabout 800 F., corrected to atmospheric pressure.

The heavy alkylate bottoms oils exhibit unusually high viscosities at100 F. compared to saturated hydrocarbon fractions produced from virginstock which have equal average molecular weights and which boil over thesame ranges. In addition, the viscosity of the heavy alkylate bottomsoils varies strongly with temperature. The vis cosity index of thesebottoms oils is very low compared to that of virgin oils. All of this isillustrated by Table I, hereinbelow, which sets out the viscosity andviscosity indexes of the approximately percent overhead fractions of aheavy alkylate oil boiling over a total boiling point range from about500 -F. to about 750 F. Table I also sets out the average molecularweight of the overhead fractions as determined by vapor pressureosmometry using a toluene solvent. In addition, the API gravity at 60 F.of each fraction is indicated, and comparative nomagraph figures forcomposite virgin stocks of like gravity are set out.

TABLE I Heavy alkylate bottoms oil Virginstock Mean Boiling averageVolume Viscosity, point range Average API boiling Viscosity percent, SSUat (initialmolecular gravity at point, SSU at OIH 100 F. V.I. final) F.weight 60 F. F 100 F.

NOTE-65 plate vacuum still. Reported boiling points corrected toatmospheric pressure.

Table I shows that the viscosities of heavy alkylate bottoms oils varyfrom about 50 SSU to about 3000 SSU to 100 F. over a very narrow totalboiling range, or viewed another way, it shows that the heavy alkylatebottoms oils have exceptional volatility for this range of viscositiesat 100 F. Table I further indicates how the viscosity index of heavyalkylate bottoms oils strongly decreases with increasing averagemolecular weight of the fraction. Viscosity indexes as low as -140 to--200 occur in the higher molecular weight fractions.

A heavy alkylate bottoms oil boiling above about 540 F. and below about800 F. is comprised of at least 90 weight percent of saturatedhydrocarbons, which are 50 to 70 weight percent naphthenes, theremainder of the saturated hydrocarbons being isoparafiins. A typicalcomposition of a heavy alkylate bottoms oil having an N.B.P. range at 10volume percent distilled of 616 F., at 50 volume percent distilled at666 F., and at 85 volume percent distilled of 728 F. is illustrated inTable II. The composition was determined by a mass spectrographicanalysis made on silica gel separated portions of the oil.

TABLE II.TYPICAL COMPOSITION OF HEAVY ALKYLATE BOTTOMS OIL yl groups tothe number of hydrogen atoms in methylene groups, as determined bynuclear magnetic resonance. For example, a simple hydrocarbon such aspropane, which has six hydrocarbon groups in methyl groups and twohydrogen atoms in methylene groups will have a branchiness ratio of 6:2or 3.0. In the complex hydrocarbons which make up the heavy alkylatebottoms oils treated according to this invention, a ratio of 3.0requires two methyl groups for each methylene group, as in propane, butthe ratio derives from a much more complicated structure involvinghighly branched naphthenic and isoparafiinic molecules. Preferably, thebranchiness ratio is from about 3.0 to about 3.5.

As Table II illustrates, the naphthenic molecules of the heavy alkylatebottoms oils are predominantly polycyclic structures. These naphthenicmolecules may be characterized according to a bicyclic ratio based onthe number of monocyclic naphthenes and bicyclic naphthenes, asdetermined by mass spectrographic techniques. The bicyclic ratio of suchnaphthenic molecules is Within the range from about 0.4 to about 0.8,and preferably, within the range from about 0.45 to about 0.6.

The branchiness ratios and bicyclic ratios of several heavy alkylatebottoms oils are set forth in Table III. Ad-

Welght percent Silica gel analysis total Sample d1t1onal blCyCllC ratiosare shown In Table VII.

saturates: TABLE III Isoparatfins 28. 7 Naphthenes 60. 9 HAB sampleTotal 89.6 1 2 3 4 Aromatics 3.8 B lling range 590-740 579-680 571-674540-674 olars 1, 6 Branchiness ratio. 2. 95 3. 65 3.17 Blcyclic ratio0.52 0.55 0.45 Grand total 100. 0

1 The manner in WhlCh the unique molecules 1n heavy ff am (136 alkylatebottoms oils influence the unusual viscosity char- ;gf acteristics ofsuch oils is illustrated by Table IV below, 1 which summarizes data fromthermal diffusions conducted 8-3; on a heavy alkylate bottoms oilshaving a N.B.P. range 1 at 10 volume percent of 622 F., at 50 volumepercent 8-32 of 672 F. and at 90 volume/percent of 770 F. (As well knownto the art, thermal diifusion separates an oil g-gg on the basis ofviscosity index rather than on the basis of 60 molecular weight, onwhich fractional distillation separas -26 3 tion is grounded.) Analysesof the saturates fractions 5,3 5,133? 50pm us from each of theseparations made by thermal diffusion igs are also included in Table IV.r g 3rlng-- 14. TABLE IV.THERMAL DIFFUSION ANALYSIS OF HEAVY gr mALKYLATE BOTTOMS 01L r ng 6 ring 6 Fraction The aromatic fractions fromsilica gel separations contain between 1 2 3 4 5 30 to 50 weight percentoi naphthenic molecules with hydrogen characterization numbers less than6. Thus, the actual aromatic concentrs- Volume percent of total 20 20 2020 20 tions are probably between 4 to 6 weight percent. 7 $11 at F. SSU1737 4%?) 8i? 2,

- 5 s -1 The saturated hydrocarbon molecules in heavy alkylate saturatesfraction;

Isoparafiins 54 30 31 28 25 bottoms 0118 have many short h ghly branchedslde chams Naphthenes 46 61 69 72 75 which are characterized by a highbranchlness ratio of i from about 2.6 to about 3.9. The branchinessratio rep- As the analysis of saturates fractions 1n Table IV inresentthe ratio of the number of hydrogen atoms in meth- 75 dicates, thefractions having the lowest viscosity indexes are those having thehighest concentrations of naphthene molecules.

The heavy alkylate bottoms oil which is hydrogen treated in accordancewith the invention may be any fraction or combination of fractionsthereof, including the total bottoms oil, boiling above the lower limitof 540 F. but below about 800 F., and having a viscosity within therange from about 75 SSU to about 3000 SSU at 100 F. and a viscosityindex within the range from about to about -200. Preferably, the heavyalkylate bottoms oil has a nominal viscosity at 100 F. of 250 SSU or 500SSU and a viscosity index within the range from about 50 to about 90. Aheavy alkylate bottoms oil with a nominal viscosity at 100 F. of 250 SSUsuitably may range in viscosity from about 200 SSU to about 300 SSU at100 F., and will generally boil within the range from about 620 F. toabout 680 F. with a 50% distillation point within the range from about640 F. to about 660 F. A heavy alkylate bottoms oil with a nominalviscosity at 100 F. of 500 SSU suitably may range in viscosity fromabout 450 SSU to about 550 SSU at 100 F. and will generally boil withinthe range from about 640 F. to about 800 F with a 50% distillation pointwithin the range from about 690 F. to about 720 F. The branchiness ratioof these preferred oils is within the range from about 2.6 to about 3.9.They have a bicyclic ratio of from about 0.4 to about 0.8.

In order to be used as a base oil in cosmetic oil formulations, it ishighly desirable that a specialty oil have a low content of aromaticcompounds. For example, USP Class A white oils, which are often used ascosmetic base oils, have a very low aromatics content, as evidenced bythe fact that USP Class A white oil specifications require that the oilnot have a DMSO extract UV absorbance exceeding 0.1 in any of the rangesof 260319 m 320- 329 m and 330-350 mg. Technical white oils, which aresuitable for use in topical cosmetics, are required to have 21 DMSOextract UV absorbance of no more than 4.0 for the range of 280-289 mu,3.3 for the range 290-299 mg, 2.3 for the range of 300-329 mg and 0.8for the range 330-350 mg. The hydrogen treatment accorded the heavyalkylate bottoms oil in this invention provides the heavy alkylatebottoms oil with a low aromatic compounds content making it suitable forvarious cosmetic applications. Preferably, as a result of the hydrogentreatment, the oil produced has a DMSO extract UV absorbance no greaterthan that specified (above) for a technical white oil. Most preferably,the hydrogen-treated heavy alkylate bottoms oil has a DMSO extract UVabsorbance within the ranges specified (above) for a USP Class A whiteoil.

Hydrogen refining the heavy alkylate bottoms oil The heavy alkylatebottoms oil is hydrogen refined in the presence of a sulfur-insensitivecatalyst to reduce sulfur and nitrogen in the oil to levels which willpermit the oil to be hydrogenated in the presence of a sulfur poisonableGroup VIII metal hydrogenation catalyst to the extent that the oil meetsthe aforesaid criteria. Suitably, the hydrogen-refining conditions areadjusted to reduce sulfur levels to less than about 40 p.p.m., andpreferably, to 20 p.p.m. or less of reducible sulfur compounds(expressed as sulfur). There are many sulfur-insensitive catalysts whichmay be used, typical sulfur-insensitive catalysts being cobaltmolybdate, molybdenum disulfide, molybdenum oxides and the like.Ordinarily, cobalt molybdate on a suitable support such as alumina ispreferred, in amounts of from about 1 to about 5 weight percent cobaltand from about 5 to about weight percent molybdenum both expressed asoxides, e.g. 3.7 weight percent cobalt oxide and 13.1 weight percentmolybdate oxide. Suitable hydrofining conditions include a temperaturewithin the range of from about 400 to about 700 F., preferably, withinthe range of from about 500 to about 600 F. and most advantageously,from about 500 to about 575 F. Below about 400 F., the temperature isinsufficient to satisfactorily remove sulfur and improve color in theoil, and above about 700 F., severe cracking of the naphthenic moleculesoccur, resulting in viscosity reduction in the oil. Quality isprogressively improved, and cracking is reduced or eliminated byoperating at the more preferred temperatures.

A suitable hydrofining hydrogen pressure is from about 150 to about 2000p.s.i.g., preferably within the range from about 500 to about 1000p.s.i.g., and most preferably about 600 p.s.i.g. Below about 150p.s.i.g., the pressure is insufficient to improve sulfur reduction andcolor improvement, and above about 2000 p.s.i.g., the pressure levelsbecome uneconomical. A suitable hydrogen-treat rate occurs between aboutand about 1000 s.c.f./bbl., preferably, from about 450 to about 800s.c.f./bbl., and most preferably at about 500-700 s.c.f./bbl. Belowabout 100 s.c.f./bbl., quality is insufiiciently improved in the productand above about 1000 s.c.f./bbl., no further improvement in productquality is noted. Hydrogen consumption ranges from about 2 to about 15s.c.f./bbl.

A suitable liquid hourly space velocity for the hydrofining processoccurs within the range from about 0.1 to about 10 volumes of oil pervolume of catalyst per hour, preferably within the range from about 0.5to about 3.0 v./v./hr., and most preferably, between about 2.0 and about3.0 v./v./hr. Below about 0.1 v./v./hr., the liquid hourly spacevelocity is uneconomical, and above about 10 v./v./hr., the throughputis too rapid for sufficient improvement in sulfur reduction and for odorand color improvement.

Hydrogenation of the heavy alkylate bottoms oil The hydrogen-refinedheavy alkylate bottoms oil is reacted with hydrogen in a hydrogenationzone in contact with a metal from Group VIII of the Periodic Table, e.g.nickel, platinum, paladium, or rhodium, preferably nickel. Thehydrogenation catalyst is normally used either in granular or pelletform in a fixed bed. A typical supported nickel hydrogenation catalystis nickel-kieselguhr. Suitable hydrogenation conditions include atemperature within the range of from about 400 to about 600 F., and mostpreferably about 500 F. Temperatures above about 650 F. produce severecracking of the naphthenic molecules and reduce the vicosity of the oilproduced. The lower viscosity oils within the 75 to about 3000 SSU at100 F. range may be treated at the lower temperatures indicated.

A suitable hydrogenation pressure occurs within the range of from about300 to about 3000 p.s.i.g., preferably from about 500 to about 1800p.s.i.g. Below about 300* p.s.i.g., the pressure is insufiicient toeffect satisfactory hydrogenation. Pressure levels greater than about3000 p.s.i.g. are uneconomical. A suitable hydrogen-treat rate occurswithin the range from about 300 to about 2500 s.c.f.bbl. of the oil, apreferred level being from about 800 to about 1000 s.c.f./bbl. Hydrogenconsumption ranges from about 10 to about 35 s.c.f./bbl. A suitableliquid hourly space velocity occurs within the range from about 0.1 toabout 3.0 volumes of oil per volume of catalyst per hour, preferablyWithin the range from about 0.20 to about 1.0 v./v./hr., and mostpreferably, between about 0.25 and 0.67 v./v./hr. Below about 0.10v./v./hr., the process is uneconomical and above about 3.0 v./v./hr.,the quality of the product is insufficiently improved in terms ofreduced aromatics content and level of odor and color.

DESCRIPTION OF THE DRAWING The drawing is a schematic diagram of apreferred mode of carrying out the present invention.

DESCRIPTION OF A PREFERRED EMBODIMENT Referring to the drawing,reference numeral 11 designates a charge line through which a heavyalkylate stream is introduced into a distillation zone 12, whichsuitably is a fractionation tower equipped with a heating element 13,suitably a steam coil or a furnace, for volatilizing the charge, andhaving baffle-type devices, suitably plates or other packing which bringliquid condensate into intimate counter-current contact with a risingvapor, as well known to the art. Heavy alkylate fractions boiling belowabout 540 F. are removed by overhead line 14. The heavy alkylate bottomsoils boiling above 540 F. are removed through line 15 and charged to asecond distillation zone 16 constructed similarly to distillation zone12. Distillation zone 16 is operated to recover a fraction of the heavyalkylate bottoms oil which will provide a desired viscosity. Forexample, to obtain a heavy alkylate bottoms oil having a nominalviscosity at 100 F. of 500 SSU, the heavy alkylate bottoms fractionboiling below, e.g., about 660 F. is taken overhead by line 17 forstorage in the holding tank (not shown), and the portion of the heavyalkylate bottoms oil boiling, e.g., above about 780 F. is withdrawn by abottoms line 18. The distillation cut of desired viscosity, in this casea nominal viscosity of 500 SSU at 100 F. and boiling over the range fromabout 660 F. to 780 F., is discharged from distillation zone 16 by line19 and charged to a hydrogen-refining zone 20.

In hydrogen-refining zone 20, hydrogen is introduced through line 21controlled by valve 22 to provide an amount of hydrogen within the rangeof from about 500 to about 600 s.c.f./bbl. of the distillation cutcharged to the hydrogen-refining zone 20. The distillation cut from line19 is passed across a sulfur-insensitive catalyst, preferably cobaltmolybdate, at a liquid hourly space velocity of from about 0.5 to about3.0 v./v./hr. under hydrogen pressures within the range of from about500 to about 1000 p.s.i.g. and at temperatures within the range of fromabout 500 F. to about 600 F. For a 500 SSU distillation cut, suitablehydrogen-refining conditions include a temperature of 500-550 F., a LHSVof 2.0-3.0, a hydrogen pressure of 600 p.s.i.g., and a hydrogen-treatrate of 500 s.c.f./bbl. Hydrogen uptake is generally about 2-15s.c.f./bbl.

As withdrawn from hydrogen-refining zone 20 by line 23, thehydrogen-refined heavy alkylate bottoms oil has a sulfur content of lessthan about 20 p.p.m., desirably less than about p.p.m., preferably about1-3 p.p.m.,

The hydrogen-refined oil withdrawn by line 23 is introduced intohydrogenation zone 24, into which hydrogen is passed through a line 25controlled by a valve 26 there to provide a hydrogen-treat rate withinthe range of from about 500 to about 1000 s.c.f./bbl. of the heavy genpressure of 1500 p.s.i.g. and a hydrogen-treat rate of 800 s.c.f./bbl.

The hydrogenated oil withdrawn from hydrogenation zone 24 by line 27 hasa boiling range Within the limits from about 540 F. to about 800 F., aviscosity within the range of from about 75 to about 3000 SSU at 100 F,a viscosity index within the range of from about 0 to about 200, aSaybolt color of no more than +25, and an aromatics compound content, asevidenced by UV absorption from a DMSO extract, comparable to that ofwhite oils, most preferably of Class A white oils.

The invention is further illustrated in the following examples, which intheir details are not intended to limit the scope of the invention.

EXAMPLES l-3 Examples 1-3 illustrate suitable hydrogen-refining andhydrogenation conditions for treating heavy alkylate bottoms oilsformulated to have nominal viscosities at 100 F. of 150 SSU (Example 1),500 SSU (Example 2), and 1200 SSU (Example 3). The three viscosity heavyalkylate bottoms oils were prepared by blending contiguous overheadfractions from the crude assay illustrated in Table V, using viscosityblending charts to estimate the upper and Transferred charge to 15theoretical plate, 5:1 reflux ratio vacuum still.

Thus, the 9895 percent fraction was used for the 1200 vis oil; the 75-80percent through 90-95 percent cuts inclusive were used to prepare the500 vis oil; and the 65.5 percent and 65.5-75 percent fractions wereused to prepare the 150 vis oil.

The blended 150, 500 and 1200 vis oils were then hydrogen refined andhydrogenated using the process condialkylate bottoms oil. Inhydrogenation zone 24, the oil 1s 50 tions set forth in Table VI.

TABLE VI 500 Vis, 2nd pass 1,200 Vis 113 137 147 500 Vis, Product VisVis Vis 1st pass 450 500 1st pass 2nd pass 3rd pas Hydrogen-refiningconditions-catalyst, Nalco 471 (CoMo):

Temperature, F 600 575 575 500 LHSV 1.0 1.0 2.0 2.0 Hz pressure,p.s.i.g. 600 600 600 I12 flow, s.e.f./bbl 500 500 500 Hydrogenationeonditionscatalyst NiT104: Temperature, F 400 400 400 425 450 500 430450 500 LHSV 0. 67 0- 67 0- 67 0. 67 0. 67 0. 67 0. 67 0. 67 0. 67 H2pressure, p.s.i.g 800 800 800 800 800 1, 500 800 800 1, 500 Hz flow,s.c.f./bl31 800 800 800 800 800 800 800 800 800 contacted with a GroupVIII metal hydrogenation catalyst, preferably nickel on a kieselguhrsupport at a temperature within the range of from about 400 F. to about600 F. under a hydrogen pressure within the range of from about 500 toabout 2000 p.s.i.g. at a liquid hourly space velocity within the rangeof from about 0.20 to about 1.0 v./v./hr., resulting in a hydrogenuptake of less than about 10-35 s.c.f./bbl. Suitable hydrogenationconditions for a 500 SSU heavy alkylate bottoms oil are Thehydrogenation catalyst was a Harshaw 104-T tabulated nickel catalystwhich contains 58 percent nickel on kieselguhr with a ratio of reducedtotal nickel of 0.60- 0.65. The hydrogen-refining catalyst was Nalco471, a cobalt molybdate catalyst on an alumina substrate in which 1 to 3weight percent is cobalt, expressed as oxides and 5 to 10 Weight percentis molybdate, expressed as oxides. Post reactor stripping was usedfollowing hydrogen refining. The hydrogenated oils were not stripped. Inthe case a temperature of 500 F., a LHSV of 0.330.5, a hydroof the 150vis oils, initial hydrogen-refining conditions caused excessivecracking, resulting in a 113 vis oil. Cracking was satisfactorilycontrolled for the 150 vis oil by reducing reactor temperature andincreasing the liquid hourly space velocity, as indicated in Table VI.The conditions used to hydrogen refine the 500 vis oil and the 12 visoil produce no cracking difficulties.

The hydrogen-refined oils from the 150 vis formulation temperature torecover a 90 volume percent o verhead fraction. This fraction was thenhydrogenated over fresh Harshaw nickel T-l04 catalyst at 400 F., usingan LHSV of 0.5 v./v./hr., a hydrogen-treat rate of 1000 s.c.f./bbl. anda hydrogen pressure of 800 p.s.i.g. The hydrogenated oil had thefollowing inspection:

were hydrogenated at 400 F. and 0.67 liquid hourly space TABLE V111velocity, producing Oils on one pass which were capable of I i Example 4passing the DMSO extract UV absorption specification for 10 Sulfur, ppm.13 Class A white oils of no more than 0.1 in the 260319, Nitrogen,p.p.m. 320-329 and 330-350 m ranges, as set forth in the Jou Color,Saybolt +30 nal of Association of Oflicial Agricultural Chemists, vol-Flash, F.(COC) 350 45, p. 66 (1962). However, with the 500 viscosity and1200 Pour point, F. viscosity oils, it was necessary to use severalpasses of Viscosity, SSU: increasing hydrogenation severity to improvethe color and 100 367 DMSO UV absorbance of those oils, as indicated inTables 210 F. 46.2 VI and VII. Table VII details the inspections of theoils Viscosity index -64 produced under the conditions of Table VI.Specific gravity, 60 F. .8576

TABLE V1! 500 Vis, 2nd pass 1,200 Vis 113 137 147 500 Vis, Product VisVis Vis 1st pass 450 500 1st pass 2nd pass 3rd pass N B.P., F

10% 544 582 530 665 645 673 a 50%.-- 620 634 629 716 694 735 90%.--- 673680 678 780 755 793 Viscosity,

100 F 113 137 147 425 464 444 1,139 1,115 1, 054 200 F 37. 6 39. 5 48.348. 9 48. 4 60. 7 60. 2 Viscosity index 52 68 -58 57 -55 -90 --83 Color,Saybolt--. +30 +30 +30 +26 +29 +15 +18 +25 Sulfur, p.p.m 1 1 1 1 1 1 9 11 Nitrogen, p.p.m 1 1 1 1. 7 1. 3 1 11 4 2 DMSO extract UV absorbance, m

260 27 .000 .000 .000 1.265 .373 .045 12.95 1.67 .148 000 000 .000 1.263 373 .050 9. 400 1. 67 .148 .015 01 .005 1. 055 .305 .045 7. 500 1.30 125 .03 .03 .019 .596 .194 .072 6.300 .820 .04 009 008 008 118 0.0370.017 1. 125 155 .02 Pour point, F 30 15 -5 Aniline point, F 211 215 21321s 219 a a Flash point (000), F 255 270 300 345 Bromine No 3. 2 1. 4 3.7 7. 6 13.6 Clay gel analys saturates- 96.8 98. 5 98.1 96. 8 97. 5 98.194. 1 Aromatics 3. 2 1. 5 1. 9 3. 2 2. 5 1. 9 5.9 Polars. 0.0 0.0 0.00.0 0.0 0.0 0.0 saturates type: 6

Igopavafiins 56. 6 50. 6 57. 0 Naphthenes:

1 rin 12.1 16. 2 9. 8 ,155 19.5 21.6 19.8 3 rin 10. 2 9. 4 12. 3 4rin 1. 0 2. 1 1. 0 5 rin 0. 7 0. 1 0. 1 6 ring 0. 0 0.0 0.0

Total 0.34 0.30 0.36 1. 24 0.70 0. 3.64 1.64 0.63

Bicyclic ratio. 0.62 0. 75 0.

1 Specifications for Class A white oil are 0.1 for the following myranges: 260319; 320-329; 330-350. 3 Essentially identical to reported500 vis values. 3 Essentially identical to reported 1,200 vis values. 4Clay gel aromatics contain nonaromatie naphthenes. 5 Low resolution massspectrometer. 6 Aromatics content relative. Values are not absoluteconcentrations. The 500 vis oil met UV absorption specifications forN.B.P. Range, F.: Class A white oils. The 1 200 vis oil met UVabsorption 10% 585 specifications for technical white oils. Based on there- 50% 673 sults of the inspections from the finished 1200 vis oil, 90%770 the following hydrogenation conditions should produce Aniline Pt. F.217 even better DMSO UV absorbance values and very good DMSO Absorbance,m color for heavy alkylate bottoms oils of such high vis- 280-289 0.104cosities: a temperature of 500 F., a LHSV of 0.25-0.50, 290-299 0.080 ahydrogen pressure of 1500 p.s.i.g., and a hydrogen-treat 3004129 0.035rate of 800 s.c.f./bbl. 330-350 0.007

EXAMPLE 4 This example illustrates the low toxological properties whicha heavy alkylate bottoms oil hydrogen treated in accordance with thisinvention possesses.

A heavy alkylate bottoms oil boiling above about 585 F. was distilled ina vacuum column containing 15 theoretical plates with a 5:1'refluxratio, maintaining constant boilup by reducing column pressure and/orincreasing The hydrogenated oil was then tested for toxicity and dermalirritation. An acute oral LD 50 in rats was determined by administeringgraded doses of the oil to groups of albino rats.-The animals wereobserved for 14 days after dosing. For acute dermal LD 50 and dermalirritancy determinations, a group of albino rabbits was given a singleapplication of undiluted hydrogenated oil at graded dosage levels. Theapplication site was covered with an occlusive (impervious) binder for24 hours, and

the animals were observed for 14 days. Acute eye irritation was alsodetermined on rabbits using 0.1 ml. of the hydrogenated oil. All animalswere observed for 7 days and the eyes were graded for irritancy.Repeated dermal toxicity and irritation studies were performed inrabbits. Undiluted material was applied to the skin of albino rabbitsfive days a week for two weeks at two dosage levels. Clinical studiesand microscopic sight examination of selected tissues were also carriedout. The results of these tests indicated that the hydrogenated oil hasa very low oral toxicity with an LD 50 greater than 10 grams perkilogram. The oil could not be classified as either a skin or eyeirritant.

From the foregoing, it will now be apparent that a colorless andodorless specialty oil having a viscosity within the range from about 75SSU to about 3000 SSU at 100 F., a viscosity index within the range fromabout to about 200, and a very low aromatic compounds content, asevidenced by DMSC extract UV absorption data, may be prepared byhydrogen refining and then hydrogenating a heavy alkylate bottoms oil ofapproximately the same viscosity and viscosity index desired within suchranges and having a boiling range within the limits from about 540 F. toabout 800 F., employing the hydrogenrefining and hydrogenatingconditions described. The low DMSO extract UV absorptions and the loworal toxicities and failure of the hydrogen-treated heavy alkylatebottoms oil to act as a skin or eye irritant make the oil particularlysuitable as a cosmetic oil. Thus, this invention provides a cosmetic oilhaving a viscosity at 100 F. greater than 500 SSU and up to about 3000SSU. Moreover, within the viscosity at 100 F. ranges from 75 SSU toabout 500 SSU, it provides a cosmetic oil having a viscosity index lowerthan any cosmetic oil heretofore known. In combination, the viscositycharacteristics of this oil, as they range from 75 SSU to 3000 SSU at100 F. with a correspondent viscosity index within the range from about0 to about -200 provide an oil which, when warmed from room temperatureto close to 100 F. by application to the body, becomes more fluid andhas a greater cosmetic feel than any cosmetic oil heretofore known.

Having fully disclosed and particularly pointed out my invention, thoseskilled in the art will now be able to make various changes andmodifications which nevertheless will fall within the spirit and scopeof my invention as hereinafter claimed.

I claim:

1. A method of preparing a colorless and odorless oil useful as acosmetic oil, comprising:

(a) reacting a heavy alkylate bottoms oil having a boiling range withinthe limits from about 540 F. to about 800 F., a viscosity within therange of from about 75 SSU to about 3000 SSU at 100 F., and a viscosityindex within the range from about 0 to about 200 with hydrogen in ahydrogen-refining zone in the presence of a sulfur-insensitive catalystunder hydrogen-refimng conditions including:

.a temperature within the range from about 400 to about a hydrogenpressure within the range from about 150 to about 2000 p.s.i.g.,

a liquid hourly space velocity within the range from about 0.1 to about3.0 v./v./hr., and

a hydrogen-treat rate within the range from about 100 to about 1000s.c.f./bbl. of said heavy /alkylate bottoms oil, and

(b) reacting the hydrogen-refined heavy alkylate bottoms oil withhydrogen in the presence of a Group VIII metal hydrogenation catalystunder hydrogenation conditions which include:

a temperature within the range from about 300 F. to about 650 F.,

a hydrogen pressure within the range from about 300 to about 3000p.s.i.g.,

a liquid hourly space velocity within the range of from about 0.1 toabout 3.0 v./v./hr., and

a hydrogen-treat rate within the range from about 300 to about 2500s.c.f./bbl. of said hydrogenrefined heavy alkylate bottoms oil.

2. The method of claim 1 in which said heavy alkylate bottoms oil has abranchiness ratio within the range from about 2.6 to about 3.9.

3. The method of claim 1 in which said heavy alkylate oil has a bicyclicratio of from about 0.4 to about 0.8.

4. The method of claim 1 in which said heavy alkylate bottoms oil has aviscosity within the range from about SSU to about 1500 SSU at 100 F.and wherein said hydrogen-refining conditions include:

(a) a temperature within the range from about 500 F.

to about 600 F.,

(b) a liquid hourly space velocity within the range from about 0.5 toabout 3.0 v./v./hr.,

(c) a hydrogen pressure within the range from about 500 to about 1000p.s.i.g., and (d) a hydrogen-treat rate within the range from about 450to about 800 s.c.f./bbl. 5. The method of claim 4 in which saidsulfur-insensitive catalyst is cobalt molybdate.

6. The method of claim 1 in which said hydrogenrefined heavy alkylatebottoms oil has a viscosity within the range from about 100 SSU to about1500 SSU at 100 F. and wherein said hydrogenation conditions include:

(a) a temperature within the range from about 400 F. to about 600 F.,

(b) a liquid hourly space velocity within the range from about 0.2 toabout 1.0',

(c) a hydrogen pressure within the range from about 500 to about 2000p.s.i.g., and

(d) a hydrogen-treat rate within the range from about 500 to about 1000s.c.f./bbl.

7. The method of claim 6 in which Group VIII metal hydrogenationcatalyst is a nickel catalyst.

8. The method of claim 1 wherein said heavy alkylate bottoms oil has aboiling range within the limits from about 640 F. to about 800 F. with a50% distillation point within the range from about 690 F. to about 720F., and has a viscosity within the range from about 450 SSU to about 550SSU at 100 F. and a viscosity index within the range from about 50 toabout -90.

9. The method of claim 8 in which said hydrogen refining conditionsinclude:

(a) a temperature within the range from about 500 F. to about 600 F.,

(b) a liquid hourly space velocity within the range from about 0.5 toabout 3.0 v./v./h.r., (c) a hydrogen pressure within the range fromabout 500 to about 1000 p.s.i.g., and

(d) a hydrogen treat rate within the range from about 450 to about 800s.c.f./bbl.,

and wherein said hydrogenation conditions include:

(a) a temperature within the range from about 400 F. to about 600 F.,

(b) a liquid hourly space velocity within the range from about 0.2 toabout 1.0,

(c) a hydrogen pressure within the range from about 500 to about 2000p.s.i.g., and

(d) a hydrogen treat rate within the range from about 500 to about 1000s.c.f./bbl.

10. The method of claim 1 wherein said heavy alkylate bottoms oil has aboiling range within the limits from about 620 F. to about 680 F. with a50% distillation point within the range from about 640 F. to about 660F., said oil having a viscosity within the range from about 200 SSU toabout 300 SSU at 100 F., and a viscosity index within the range fromabout 50 to about 90.

11. The method of claim wherein said hydrogen refining conditionsinclude:

(a) a temperature within the range from about 500 F to about 600 F.,

(b) a liquid hourly space velocity within the range from about 0.5 toabout 3.0 v./v./hr., (c) a hydrogen pressure Within the range from about500 to about 1000 p.s.i.g., and

(d) a hydrogen treat rate within the range from about 450 to about 800s.c.f./bbl.,

and wherein said hydrogenation conditions include:

(a) a temperature within the range from about 400 F to about 600 'F.,

(b) a liquid hourly space velocity within the range from about 0.2 toabout 1.0,

(c) a hydrogen pressure within the range from about 500 to about 2000p.s.i.g., and

(d) a hydrogen treat rate within the range from about 500 to about 1000s.c.f./bbl. 12. A colorless and odorless heavy alkylate oil boilingWithin the range from about 640 F. to about 800 F. with a 50%distillation point within the range from about 690 F. to about 720 F.,and further having:

a viscosity within the range from about 450 SSU to about 550 SSU at 100F.,

a viscosity index within the range from about 50 to about 90,

a branchiness ratio within the range from about 2.6

to about 3.9,

a bicyclic ratio of from about 0.4 to about 0.8,

a Saybolt color of at least +25, and

a DMSO extract UV absorbance of no more than about 4.0 for 280-289 mg,3.3 for 290-299 mg, 2.3 for 300-329 m and 0.8 for 330-350 mg.

13. The oil of claim 12 having an LD 50 oral toxicity of greater than 10grams per kilogram of body weight.

14. The oil of claim 12 having a DMSO extract UV 14 absorbance of nomore than 0.1 in any of the millimicron ranges of 260-319, 320-329 and330-350.

15. A colorless and odorless heavy alkylate oil boiling within thelimits from about 620 F. to about 680 F. and having a distillation pointwithin the range from 640 F. to 660 F., and further having:

a viscosity within the range from about 150 SSU to about 250 SSU at F.,

a viscosity index within the range from about -50 to about 90,

a branchiness ratio within the range from about 2.6

to about 3.9,

a bicyclic ratio within the range from about 0.4 to

about 0.8,

a Saybolt color of at least +25, and

a DMSO extract UV absorbance of no more than 4.0

for 280-289 m 3.3 for 29-299 m 2.3 for 300- 329 I'll 1., and 0.8 for330-350 mg.

16. The oil of claim 15 having an LD 50 oral toxicity of greater than 10grams per kilogram of body weight.

17. The oil of claim 15 having a DMSO extract UV absorbance of no morethan 0.1 in any of the millimicron range of 260-319, 320-329, and330-350.

References Cited UNITED STATES PATENTS 2,915,452 12/1959 Fear 208-1443,121,678 2/1964 Behyzner et a1. 208212 3,328,293 6/1967 Brenken 208-1433,459,656 8/1969 Rausch 208-144 HERBERT LEVINE, Primary Examiner US. Cl.X.R. 208-49, 89, 144

